Ziegler-Natta polymerization of

olefins - stereoselectivity
CHEM 462: Inorganic/Organometallic
Chemistry
Haomiao Xie & Xu Ye
Professor: Dr. Marcetta Y. Darensbourg

1
 Outline
1. Introduction of polymerization and history of Ziegler-Natta Catalysts.
1.1 Overview of polymer and polymerization.
1.2 coordination polymerization and Ziegler-Natta Catalysts

2. Mechanism of Ziegler-Natta polymerization.

2.1 The Cossee Mechanism
2.2 The Green-Rooney Mechanism
2.3 The evidence supporting the Cossee Mechanism

3. Effect factor of Ziegler-Natta polymerization

3.1 Effect factors of 1,2-insertion
3.2 Effect factors of beta-elimination

4. Stereoselectivity of Ziegler-Natta Catalysts

4.1 Categories of Stereoselective Ziegler-Natta Catalysts
4.2 Mechanism and effect factors of Stereoselective Ziegler-Natta Catalysts

5. Conclusion

2
 Outline
1. Introduction of polymerization and history of Ziegler-Natta Catalysts.
1.1 Overview of polymer and polymerization.
1.2 coordination polymerization and Ziegler-Natta Catalysts

2. Mechanism of Ziegler-Natta polymerization.

2.1 The Cossee Mechanism
2.2 The Green-Rooney Mechanism
2.3 The evidence supporting the Cossee Mechanism

3. Effect factor of Ziegler-Natta polymerization

3.1 Effect factors of 1,2-insertion
3.2 Effect factors of beta-elimination

4. Stereoselectivity of Ziegler-Natta Catalysts

4.1 Categories of Stereoselective Ziegler-Natta Catalysts
4.2 Mechanism and effect factors of Stereoselective Ziegler-Natta Catalysts

5. Conclusion

3
 Overview
Polymer: large molecule, composed with many
repeated subunits.
Use:
Natural: DNA, protein
Artificial: polystyrene,
polyvinyl chloride (PVC)

4
http://en.wikipedia.org/wiki/Polymer#mediavi
ewer/File:ADN_animation.gif
Artificial Polymer Products
 World's demand for PE and PP

Callais, P. Outlook for PE and PP Resins. 16th Annual Canadian Plastics Resin Outlook Conference. Available
6 online:
http://www.canplastics.com/conference/2011Presentations/ 5._Peter_Callais.
 Overview
Polymerization reaction
Step growth: polymers formed by the stepwise reaction
between functional groups of monomers

Chain growth: linking together of molecules incorporating

double or triple carbon-carbon bonds.
radical addition polymerization
cationic addition polymerization
anionic addition polymerization
Coordination polymerization (olefin binding/alkyl insertion)

7
Coordination Polymerization and Ziegler-Natta Catalysts

Coordination polymerization: an addition

polymerization in which successive monomers
are added to the organometallic active center.
Examples are:
ROMP (Ring open metathesis polymerization)
Polymerization catalyzed by Ziegler-Natta catalyst
Polymerization catalyzed by Late Transition Metal
Complexes catalyst

8
 Ziegler-Natta Catalyst: History
1953 Karl Ziegler polymerizes ethene into high MW-HDPE (high
density polyethylene) with catalyst based on TiCl4, and Et2AlCl as
co-catalyst.
Giulio Natta, utilizes Zieglers catalyst to produce PP.
1963 Ziegler and Natta are awarded the Nobel Prize
1973 2nd generation Ziegler-Natta catalysts introduced with
TiCl3 purple phases at lower temperatures.
1975-1978 3rd generation catalysts supported on MgCl2
commercialized by many companies.
1977-1980 Kaminsky and Sinn discover high activity metallocene
single-site catalysts (SSCs) using methylaluminoxane (MAO) as co-
catalyst.
1991 Fourth generation Ziegler-Natta catalysts based on
aluminium-oxane activated metallocene complexes used.
1997 Montel (or Lyondell Basell) commercialize PP based on 5th
generation Ziegler-Natta catalyst that use 1.3-diethers, and
succinate as donors.
9
A. Shamiri, M. H. Chakrabarti, S. Jahan, M. A. Hussain, W. Kaminsky, P. V. Aravind and W. A. Yehye, Materials 2014, 7, 5069-5108.
 Nobel Prize: 1963

Karl Ziegler, Germany Giulio Natta, Italy

Prize motivation:
"for their discoveries in the field of the chemistry and technology of high polymers"
10
Giulio Natta - Facts". Nobelprize.org. Nobel Media AB 2014. Web. 17 Nov 2014. <http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1963/natta-facts.html>
 Single Site Metallocene Catalysts: Living Polymerization

11
1. A. Shamiri, M. H. Chakrabarti, S. Jahan, M. A. Hussain, W. Kaminsky, P. V. Aravind and W. A. Yehye, Materials 2014, 7, 5069-5108.
 Outline
1. Introduction of polymerization and history of Ziegler-Natta Catalysts.
1.1 Overview of polymer and polymerization.
1.2 coordination polymerization and Ziegler-Natta Catalysts

2. Mechanism of Ziegler-Natta polymerization.

2.1 The Cossee Mechanism
2.2 The Green-Rooney Mechanism
2.3 The evidence supporting the Cossee Mechanism

3. Effect factor of Ziegler-Natta polymerization

3.1 Effect factors of 1,2-insertion
3.2 Effect factors of beta-elimination

4. Stereoselectivity of Ziegler-Natta Catalysts

4.1 Categories of Stereoselective Ziegler-Natta Catalysts
4.2 Mechanism and effect factors of Stereoselective Ziegler-Natta Catalysts

5. Conclusion

12
 2.1 The Cossee Mechanism
P
P
H
CH2 Ligand association H
+ C

M R M

1,2-insertion

P
P
H
H2C R
C
R
H
M
M

P.Cossee,J.Catal.,1964,3,80 and E.J.Arlman and P.Cossee,J.Catal.,1964,3,99

Brookhart, M.; Green, M.; Wong, L. L. Prog. Inorg. Chem. 1988,36, 1-124.
13
Brookhart, M.; Volpe, A. F., Jr.; Lincoln, D. M.; Horva th, I. T.;Millar, J. M. J. Am. Chem. Soc. 1990, 112, 5634-
2.2 The Green-Rooney Mechanism

K.J.Ivin,J.J.Rooney,C.D.Stewart, M.L.H. Green, and J.R. Mahtab, J. Chem. Soc, Chem. Commun., 1978, 604
M.L.H. Green, Pure Appl. Chem., 1978,100,2079

14
Chain Termination and Chain Transfer Steps

15
Kinetic Isotope Effect

D2C CD2 Cp2(Et)(Cl)Ti/EtAlCl2

+ CH3CH2(CX2CX2)nH
H2C CH2
X= H, D
1:1 H:D = 1:1

kH > kD

Conclusion: Lack of KIE indicates no C-H bond

breaking in RDS
J.Soto,M.Steigerwald, and R.H. Grubbs, J. Am. Chem. Soc. , 1982,104,4479
16
Kinetic Isotope Effect, continued
Green-Rooney Mechanism
Al Al Al
H
Cl H Cl Cl H
D D
Cp2Ti Cp2Ti Cp2Ti
H H D

Al Al
ClH H ClH H
Product Ratio is 1:1
Cp2Ti 1 Cp2Ti 1
"Cis"
"trans"
2 2

H H

H
Cp2Ti
H Cp2Ti Cl D
H Cl H Al
D
Cp2Ti Al

HCl D H H
Al
L.Clawson,J.Soto,S.L.Buchwald,M.L.Steigerwald,and R.H.Grubbs, J. Am. Chem. Soc.,1985,107,3377 17
"Stereochemical" Isotope Effect
Cossee Mechanism
Al Al
Cl H Cl H Al
D D ClH
Cp2Ti D
Cp2Ti
H Cp2Ti 1
2

H H

"Cis"

Product Ratio is 1:1

H
Cp2Ti
Al
Cp2Ti Cl D
ClH D
Cl H Al
TiCp2 1
Al
2

H H H
"trans"
L.Clawson,J.Soto,S.L.Buchwald,M.L.Steigerwald,and R.H.Grubbs, J. Am. Chem. Soc.,1985,107,3377
Conclusion: Cossee Mechanism

Negative results of Kinetic Isotope Effect

excludes Green-Rooney Mechanism
"Stereochemical" Isotope Effect shows the
Cossee Mechanism is reasonable

19
 Outline
1. Introduction of polymerization and history of Ziegler-Natta Catalysts.
1.1 Overview of polymer and polymerization.
1.2 coordination polymerization and Ziegler-Natta Catalysts

2. Mechanism of Ziegler-Natta polymerization.

2.1 The Cossee Mechanism
2.2 The Green-Rooney Mechanism
2.3 The evidence supporting the Cossee Mechanism

3. Factors that Affect Ziegler-Natta Polymerization

3.1 Effects on 1,2-insertion
3.2 Effects on -elimination

4. Stereoselectivity of Ziegler-Natta Catalysts

4.1 Categories of Stereoselective Ziegler-Natta Catalysts
4.2 Mechanism and effect factors of Stereoselective Ziegler-Natta Catalysts

5. Conclusion

20
 1,2-insertion and -Elimination

H2C CH2 H2C CH2 H2C CH2

LnM H LnM H LnM H

Insertion
-Elimination

H2C CH2 H2C CH2 H2C CH2

LnM R LnM R LnM R

21
Electronic Characteristics of Early and Late Transition Metals in
Olefin Polymerization/Oligomerization Catalysis

Catalysts for Polymerization Catalysts for Oligomerization

Ph Ph Ph
Ph
C P P

Ni H Ni
H
O O
O

d-* Interaction -elimination favored for

Stabilizing factor Ni, yielding short chains

Late Transistion Metal: Ni(II) d8

Ti(IV),Zr(IV),V(V): d0
lower Ea for -Elimination
Dynamically stable
Shell Higher Olefin Process(SHOP)

22
Bulky diimine groups impede the -Elimination

N N

Ni

Br Br

N N

Pd
O

MeO

L.K.Johnson,C.M.Killian, and M. Brookhart,J. Am. Chem. Soc.,1995,117,6414

23
 Electronic Effect of -Elimination

Spaleck, W.; Antberg, M.; Rohrmann, J.; Winter, A.; Bachmann,B.; Kiprof, P.; Behm, J.;
Herrmann, W. A. Angew. Chem., Int.Ed. Engl. 1992, 31, 1347-1350.
24
 Effect of Metal
Bond Energy of M-C and M-H

3rd row > 4th row> 5th row

1,2-insertion :

Ti < Zr < Hr Ni< Pb < Pt

-Elimination:

Ti > Zr > Hr Ni > Pb > Pt

25
 Outline
1. Introduction of polymerization and history of Ziegler-Natta Catalysts.
1.1 Overview of polymer and polymerization.
1.2 coordination polymerization and Ziegler-Natta Catalysts

2. Mechanism of Ziegler-Natta polymerization.

2.1 The Cossee Mechanism
2.2 The Green-Rooney Mechanism
2.3 The evidence supporting the Cossee Mechanism

3. Effect factor of Ziegler-Natta polymerization

3.1 Effect factors of 1,2-insertion
3.2 Effect factors of beta-elimination

4. Stereoselectivity of Ziegler-Natta Catalysts

4.1 Categories of Stereoselective Ziegler-Natta Catalysts
4.2 Mechanism and effect factors of Stereoselective Ziegler-Natta
Catalysts

5. Conclusion
26
Designation of polymer stereotype

"m" for meso

"r" for racemic

Geoffrey W. Coates, Chem. Rev. 2000, 100, 1223-1252 1223 27

 Characterization of tacticity

Method:
solubility
X-ray diffraction
IR spectroscopy
thermal properties
NMR (Most Important)

(a) methyl region of the 13C NMR spectrum of atactic polypropylene

(b) Simulated 13C NMR spectrum by using -gauche effect
James E. Mark , Physical properties of polymers handbook , 2nd ed.Press. New York : Springer28,
2007 ,page 359-384
 Isotactic Polymerization

C2v : Cp2MCl2 only atactic polypropylene

or End Control Cp2TiPh2 ; (iPrCp)2TiCl2
M
Cl
isotactic or syndiotactic
Cl
(temperature dependent)
C2 Catalysts most successful :
Ligand with a bridging group
--rigid structure

29
Five Main Symmetry Catagories of Single-
site Polymerization Catalysts

Bulky Group
Cp ring

Geoffrey W. Coates, Chem. Rev. 2000, 100, 1223-1252 1225 30

Mechanism of C2 Catalysts
H
H H
MMe M
H
H H M
H H H
H Me
H
P
P
H
P
H
Me

H M H
H H P Me
Me
R R
* *
H *
H P R H
H M
H H
H H
Me Me
Me

M H P H
Me
H H
H *
R M H
Me
H H
P H
R H H
*

Me
H
H Me

31
R.H. Grubbs and G.W.Coates,Acc.Chem.Res.1996.29.85
Geoffrey W. Coates, Chem. Rev. 2000, 100, 1223-1252 1226,1227 32
 Stereoerror:

Geoffrey W. Coates, Chem. Rev. 2000, 100, 1223-1252 1226,1227

Busico, V.; Brita, D.; Caporaso, L.; Cipullo, R.; Vacatello, M.Macromolecules 1997, 30, 3971-3977.
33
Strategies for modifying bridged metallocene structure:

Modification of bridge:

Si , P , B Bridged catalysts

Modification of metalloncene ligands

Substitution and derivatives of Cp rings

Variation of the activator

Bu3Al with [PhNHMe2][B(C6F5)4]

34
 Syndiotactic Polymerization
Me

C2v : Cp*2MCl2 (M=Zr, Hf) Me Me

Me Me
Cl
Me

Syndiotactic polymer Me M

Cl
Me

Me

2 kcal/mol preference for syndiotactic versus isotactic

Me

Cs Catalysts : Regularly alternating insertion of

olefins at the enantiotopic sites

Resconi, L.; Abis, L.; Franciscono, G. Macromolecules 1992, 25,6814-6817.

35
Examples of Cs Catalysts

36
 Mechanism of Cs Catalysts

Me H
P P
H
P M
M H M H
Me *
H Me H H
H S H
H H
H
H H Me

Me H
Me H Me
H H P M
M * H
Me *
R P S H H
H *
S
H Me

37
 Hemiisotactic Polymerization
C1 Catalysts :

Two Different Coordination Sites

One isospecific site, One aspecific site

38
Mechanism of C1 Catalysts for Hemiisotactic
Polymer
Me

P M
H H
M P H
Me H
H
Me
H

isospecific site
aspecific site

Me
Me H Me
H P M
M H
Me
P H
H H
*
R
H Me

39
 Influence of substituent

Cs C1 C1
Syndiatactic Hemiisotactic Isotactic

Ewen, J. A.; Jones, R. L.; Razavi, A.; Ferrara, J. D. J. Am. Chem.Soc. 1988, 110, 6255-6256.
Ewen, J. A.; Elder, M. J.; Jones, R. L.; Haspeslagh, L.; Atwood,J. L.; Bott, S. G.; Robinson, K. Makromol. Chem.,
Macromol.Symp. 1991, 48-9, 253-295.

40
Site Epimerization

R1 R3 R1 R3

k1

M M
P P
k -1

R2 R4 R2 R4

k2 k3

chain growth chain growth

41
 Site Epimerization Induced Isotactic polymerization
R1 R3 R1 R3
One site has very bulky groups k1
(for example R3,R4), k1 << k-1 M M
P P
the other is stereospecific. k -1

R2 R4 R2 R4

k2 k3

chain growth chain growth

Ewen, J. A.; Elder, M. J.; Jones, R. L.; Haspeslagh, L.; Atwood,J. L.; Bott, S. G.; Robinson, K. Makromol. Chem.,
Macromol.Symp. 1991, 48-9, 253-295.
Ewen, J. A.; Elder, M. J. Makromol. Chem., Macromol. Symp.1993, 66, 179-190
42
 Stereoblock Polymerization
k1 and k-1 are large; S M

k1
S M

sites exchange rapidly M

P P
M
k -1

k2,k3 << k1,k-1 L M L M

Sensitive to the reaction

k2 k3
temperature
chain growth chain growth
( Isotactic block ) (Atactic block)

Gauthier, W. J.; Corrigan, J. F.; Taylor, N. J.; Collins, S.Macromolecules 1995, 28, 3771-3778.
Mallin, D. T.; Rausch, M. D.; Lin, Y. G.; Dong, S.; Chien, J. C.W. J. Am. Chem. Soc. 1990, 112, 2030-2031. 43
 Oscillating Catalysts
S L S L

k1

M M
P P
k -1

S L L S
Cs C2

k2 k3
Cs C2
chain growth chain growth
( Syndiotactic block ) (Isotactic block

Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217-219.

44
 Chain Transfer

Et(Ind)2ZrCl2 & Me2Si(Ind)2ZrCl2 : atactic - isotactic

Me2Si(Ind)2ZrCl2 & Me2C(Cp)(Fl)ZrCl2 : isotactic - syndiotactic

Geoffrey W. Coates, Chem. Rev. 2000, 100, 1223-1252 1226,1227

Chien, J. C. W.; Iwamoto, Y.; Rausch, M. D.; Wedler, W.; Winter,H. H. Macromolecules 1997, 30, 3447-3458.

Chien, J. C. W.; Iwamoto, Y.; Rausch, M. D. J. Polym. Sci. A 1999, 37, 2439-2445.
45
Przybyla, C.; Fink, G. Acta Polym. 1999, 50, 77-83.
 Conclusion
Polymers play an important part in our daily lives. Various methodologies
make it possible to synthesize polymers with different properties and
functions. Coordination polymerization, especially Ziegler- Natta catalysis,
dominates the olefin polymerization industry.
Ziegler-Natta catalysts can be categorized into heterogenous and
homogenous by their form in catalysis process. The heterogenous one is
widely used in industry while the homogenous one, single site catalysts ,
are intensely investigated for the clarity of mechanism and development
of strategies to modulate the properties of catalysts and polymers.
Ziegler-Natta catalysts with different symmetry and ligands enrich the
library of stereospecific polymers. Possibility of synthesizing different
Ziegler-Natta Catalysts for mutifunctional polymers remains to be
explored.

46
Thanks for your attention!

Questions?

47